@article{farias_rodrigues_botelho_magalhaes_raisanen_freeman_umbuzeiro_2024, title={The natural anthraquinone dye emodin: Eco/genotoxicological characterization for aquatic organisms}, volume={189}, ISSN={["1873-6351"]}, DOI={10.1016/j.fct.2024.114749}, abstractNote={Emodin is an anthraquinone secondary metabolite produced by several species of plants and fungi. Emodin is known for its pharmacological versatility, and, in the textile industry, for its good dyeing properties. However, its use in the textile industry can result in the formation and disposal of large volumes of wastewater. Emodin mutagenicity has been shown in bacteria and in human cells, but little is known about its possible toxic, genotoxic, or mutagenic effects in aquatic organisms. We have evaluated the eco/genotoxicity of emodin to aquatic organisms. Emodin was toxic to Daphnia similis (EC50 = 130 μg L-1) and zebrafish embryos (LC50 = 25 μg L-1). No toxicity was observed for Raphidocelis subcapitata, Ceriodaphnia dubia, or Parhyale hawaiensis. Additional biochemistry/molecular studies are needed to elucidate the toxic/mutagenic pathways of emodin in aquatic organisms. The PNEC value for emodin was 0.025 μg L-1. In addition to mutagenicity in the Salmonella/microsome assay, emodin was mutagenic in the micronucleus assay in the amphipod P. hawaiensis. Among the anthraquinone dyes tested to date, natural or synthetic, emodin was the most toxic to aquatic species.}, journal={FOOD AND CHEMICAL TOXICOLOGY}, author={Farias, Natalia Oliveira and Rodrigues, Amanda Rocha and Botelho, Marina Tenorio and Magalhaes, Gabriel Rampazzo and Raisanen, Riikka and Freeman, Harold S. and Umbuzeiro, Gisela de Aragao}, year={2024}, month={Jul} } @article{williams_vacchi_santos_szymczyk_umbuzeiro_freeman_2022, title={Evaluation of the Toxicological and Color Properties of Anionic Hydrophobic Monoazo Dyes for Sustainable Human Hair Coloration}, volume={10}, ISSN={["2168-0485"]}, url={https://doi.org/10.1021/acssuschemeng.1c05702}, DOI={10.1021/acssuschemeng.1c05702}, abstractNote={The design of hair dyes having environmentally benign characteristics in addition to very good durability to washing and UV light is of importance to overcome the limitations of conventional permanent hair dyes in the marketplace. As a step toward meeting this vision, we synthesized anionic azo dyes having a built-in C4, C8, or C12 alkyl chain and evaluated their hair dyeing and toxicological properties. As anticipated, the dyes increased in hydrophobicity (SlogP) with the increase in alkyl chain length. Based on prior technology, it is known that certain anionic textile dyes possessing a C12 group exhibit high affinity for wool fibers during rigorous washing in the commercial milling process. In the present study, the dye containing the C8 chain displayed the greatest uptake and the most promise as a potential permanent hair dye. Further, dyes containing a C4 or C8 carbon chain were found to be nontoxic ≤100 mg L using the crustaceans Daphnia similis and Parhyale hawaiensis as test organisms. The dye containing a C12 carbon chain provided an EC50 of 57.4 mg L–1 using D. similis, but it was nontoxic ≤100 mg L–1 to P. hawaiensis. All dyes were nontoxic using the algae Raphidocelis subcapitata, and none of the dyes exhibited mutagenicity toward the strains used.}, number={8}, journal={ACS SUSTAINABLE CHEMISTRY & ENGINEERING}, author={Williams, Tova N. and Vacchi, Francine I. and Santos, Amanda and Szymczyk, Malgorzata and Umbuzeiro, Gisela de Aragao and Freeman, Harold S.}, year={2022}, month={Feb}, pages={2593–2601} } @article{herrala_yli-oyra_albuquerque_farias_morales_raisanen_freeman_umbuzeiro_rysa_2022, title={Waterless Dyeing and In Vitro Toxicological Properties of Biocolorants from Cortinarius sanguineus}, volume={8}, ISSN={["2309-608X"]}, DOI={10.3390/jof8111129}, abstractNote={As a part of an ongoing interest in identifying environmentally friendly alternatives to synthetic dyes and in using liquid CO2 as a waterless medium for applying the resulting colorants to textiles, our attention turned to yellow-to-red biocolorants produced by Cortinarius sanguineus fungus. The three principal target anthraquinone colorants (emodin, dermocybin, and dermorubin) were isolated from the fungal bodies using a liquid–liquid separation method and characterized using 700 MHz NMR and high-resolution mass spectral analyses. Following structure confirmations, the three colorants were examined for dyeing synthetic polyester (PET) textile fibers in supercritical CO2. We found that all three biocolorants were suitable for dyeing PET fibers using this technology, and our attention then turned to determining their toxicological properties. As emodin has shown mutagenic potential in previous studies, we concentrated our present toxicity studies on dermocybin and dermorubin. Both colorants were non-mutagenic, presented low cellular toxicity, and did not induce skin sensitization. Taken together, our results indicate that dermocybin and dermorubin possess the technical and toxicological properties needed for consideration as synthetic dye alternatives under conditions that are free of wastewater production.}, number={11}, journal={JOURNAL OF FUNGI}, author={Herrala, Mikko and Yli-oyra, Johanna and Albuquerque, Anjaina Fernandes and Farias, Natalia Oliveira and Morales, Daniel Alexandre and Raisanen, Riikka and Freeman, Harold S. and Umbuzeiro, Gisela Aragao and Rysa, Jaana}, year={2022}, month={Nov} } @article{freeman_santos_chen_vendemiatti_oliveira_vacchi_vinueza_umbuzeiro_2021, title={Molecular characterization and ecotoxicological evaluation of the natural dye madder and its chlorinated products}, volume={11}, ISSN={["1614-7499"]}, DOI={10.1007/s11356-021-17388-4}, abstractNote={There has been increased interest in the use of natural dyes for textile coloration as alternatives to synthetic dyes, due to the general belief that natural dyes are more environmentally friendly. However, natural dyes have poor affinity for textiles, which can lead to high dye levels in the resultant wastewater. While chlorine treatment has proven to be effective for dye wastewater disinfection and decolorization, this process can also lead to the formation of more toxic degradation products for certain synthetic dyes. On the other hand, little information is available regarding the ecotoxicity of natural dyes and their chlorination products. To advance knowledge in this area, madder was selected due to its historical importance and wide application in the textile industry. Specifically, we sought to characterize the chlorine-induced degradation products of an aqueous madder solution and to assess their ecotoxicity. The main component of the present madder sample was Alizarin (89.8%). Chlorination led to complete decolorization, and 2-hydroxynaphthalene-1,4-dione and phthalic anhydride were identified as key degradation products. Chlorination of madder decreased toxicity to Daphnia similis (microcrustacean) 10-fold and removed the toxicity to Raphidocellis subcapitata (algae), when compared to the parent dye.}, journal={ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH}, author={Freeman, Harold S. and Santos, Tuane C. and Chen, Yufei and Vendemiatti, Josiane A. S. and Oliveira, Adria C. and Vacchi, Francine I. and Vinueza, Nelson R. and Umbuzeiro, Gisela A.}, year={2021}, month={Nov} } @article{umbuzeiro_morales_vacchi_albuquerque_szymczyk_sui_vinueza_freeman_2021, title={A promising Ames battery for mutagenicity characterization of new dyes}, volume={62}, ISSN={["1098-2280"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-85097440491&partnerID=MN8TOARS}, DOI={10.1002/em.22417}, abstractNote={AbstractWhen testing new products, potential new products, or their impurities for genotoxicity in the Ames test, the quantity available for testing can be a limiting factor. This is the case for a dye repository of around 98,000 substances the Max Weaver Dye Library (MWDL). Mutagenicity data on dyes in the literature, although vast, in several cases is not reliable, compromising the performance of the in silico models. In this report, we propose a strategy for the generation of high‐quality mutagenicity data for dyes using a minimum amount of sample. We evaluated 15 dyes from different chemical classes selected from 150 representative dyes of the MWDL. The purity and molecular confirmation of each dye were determined, and the microplate agar protocol (MPA) was used. Dyes were tested at the limit of solubility in single and concentration‐response experiments using seven strains without and with metabolic activation except for anthraquinone dyes which were tested with eight strains. Six dyes were mutagenic. The most sensitive was YG1041, followed by TA97a > TA98 > TA100 = TA1538 > TA102. YG7108 as well as TA1537 did not detect any mutagenic response. We concluded that the MPA was successful in identifying the mutagenicity of dyes using less than 12.5 mg of sample. We propose that dyes should be tested in a tiered approach using YG1041 followed by TA97a, TA98, and TA100 in concentration‐response experiments. This work provides additional information on the dye mutagenicity database available in the literature.}, number={1}, journal={ENVIRONMENTAL AND MOLECULAR MUTAGENESIS}, author={Umbuzeiro, Gisela A. and Morales, Daniel A. and Vacchi, Francine I and Albuquerque, Anjaina F. and Szymczyk, Malgorzata and Sui, Xinyi and Vinueza, Nelson and Freeman, Harold S.}, year={2021}, month={Jan}, pages={52–65} } @article{vendemiatti_camparotto_vidal_cristale_agapito_oliveira_rodrigues_montagner_umbuzeiro_prediger_2021, title={New benzotriazoles generated during textile dyeing process: Synthesis, hazard, water occurrence and aquatic risk assessment}, volume={403}, ISSN={["1873-3336"]}, DOI={10.1016/j.jhazmat.2020.123732}, abstractNote={Phenylbenzotriazoles (PBTA) can be generated unintentionally during textile dyeing factories by reduction of dinitrophenylazo dyes and their subsequent chlorination in disinfection process. Eight non-chlorinated PBTAs (non-Cl PBTA) and their related chlorinated PBTAs have been found in rivers and presented mutagenic activity. No data on their aquatic toxicity are available. In this work, two new phenylbenzotriazoles, non-Cl PBTA-9 and PBTA-9, derived from the dye C.I. Disperse Violet 93 (DV93) were synthesized and chemically/toxicologically characterized. Both compounds were more mutagenic than the parental dye in the Salmonella/microsome assay in the presence of metabolic activation (S9). Mutagenicity studies in vivo with mammals would confirm their potential hazard to humans. The two compounds were acutely toxic to Daphnia similis. We developed an analytical method to simultaneously quantify non-Cl PBTA-9, PBTA-9 and DV93 in river waters. Non-Cl PBTA-9 was found in sites under influence of textile effluents but at concentrations that do not pose risk to the aquatic life according to the P-PNEC calculated based on the acute toxicity tests. PBTA-9 was not detected in any samples analyzed. More studies on the aquatic toxicity and water occurrence of PBTAs should be conducted to verify the relevance of this class of compounds as aquatic contaminants.}, journal={JOURNAL OF HAZARDOUS MATERIALS}, author={Vendemiatti, Josiane A. Souza and Camparotto, Natalia G. and Vidal, Cristiane and Cristale, Joyce and Agapito, Estevao Vieira de Moraes and Oliveira, Adria Calotto and Rodrigues, Everton A. and Montagner, Cassiana C. and Umbuzeiro, Gisela A. and Prediger, Patricia}, year={2021}, month={Feb} } @article{zaidy_vacchi_umbuzeiro_freeman_2019, title={Approach to Waterless Dyeing of Textile Substrates-Use of Atmospheric Plasma}, volume={58}, ISSN={["0888-5885"]}, DOI={10.1021/acs.iecr.9b01260}, abstractNote={The international textile wet processing industry produces large amounts of wastewater, which if discharged into the environment could have adverse effects on aquatic life and drinking water. Effor...}, number={40}, journal={INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH}, author={Zaidy, Syed S. H. and Vacchi, Francine I. and Umbuzeiro, Gisela A. and Freeman, Harold S.}, year={2019}, month={Oct}, pages={18478–18487} } @article{umbuzeiro_albuquerque_vacchi_szymczyk_sui_aalizadeh_ohe_thomaidis_vinueza_freeman_2019, title={Towards a reliable prediction of the aquatic toxicity of dyes}, volume={31}, ISSN={["2190-4715"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-85074502142&partnerID=MN8TOARS}, DOI={10.1186/s12302-019-0258-1}, abstractNote={Abstract Background The Max Weaver Dye Library (MWDL) from North Carolina State University is a repository of around 98,000 synthetic dyes. Historically, the uses for these dyes included the coloration of textiles, paper, packaging, cosmetic and household products. However, little is reported about their ecotoxicological properties. It is anticipated that prediction models could be used to help provide this type information. Thus, the purpose of this work was to determine whether a recently developed QSAR (quantitative structure–activity relationships) model, based on ACO-SVM techniques, would be suitable for this purpose. Results We selected a representative subset of the MWDL, composed of 15 dyes, for testing under controlled conditions. First, the molecular structure and purity of each dye was confirmed, followed by predictions of their solubility and pKa to set up the appropriate test conditions. Only ten of the 15 dyes showed acute toxicity in Daphnia, with EC50 values ranging from 0.35 to 2.95 mg L−1. These values were then used to determine the ability of the ACO-SVM model to predict the aquatic toxicity. In this regard, we observed a good prediction capacity for the 10 dyes, with 90% of deviations within one order of magnitude. The reasons for this outcome were probably the high quality of the experimental data, the consideration of solubility limitations, as well as the high purity and confirmed chemical structures of the tested dyes. We were not able to verify the ability of the model to predict the toxicity of the remaining 5 dyes, because it was not possible to determine their EC50. Conclusions We observed a good prediction capacity for the 10 of the 15 tested dyes of the MWDL, but more dyes should be tested to extend the existing training set with similar dyes, to obtain a reliable prediction model that is applicable to the full MWDL. }, number={1}, journal={ENVIRONMENTAL SCIENCES EUROPE}, author={Umbuzeiro, Gisela de A. and Albuquerque, Anjaina F. and Vacchi, Francine I and Szymczyk, Malgorzata and Sui, Xinyi and Aalizadeh, Reza and Ohe, Peter C. and Thomaidis, Nikolaos S. and Vinueza, Nelson R. and Freeman, Harold S.}, year={2019}, month={Dec} }